Tetra(phenylphosphinates) of titanium and zirconium



United States Patent 3,426,050 TETRA(PHENYLPHOSPHINATES) 0F TITANIUM AND ZIRCONIUM Gerd Helmut Dahl, King of Prussia, Pa., assignor to Pennsalt Chemicals Corporation, Philadelphia, Pa., a corporation of Pennsylvania 1 No Drawing. Filed Jan. 21, 1966, Ser. No. 522,045 US. Cl. 260429.3 Claims Int. Cl. C07f 7/28; Cm 1 46 ABSTRACT OF THE DISCLOSURE Titanium and zirconium tetrakis(phenylphosphinates) useful as viscosity improvers for oils and as grease thickeners are provided having the formulae M[OP(Ph) O] and M[OP(R)(Ph)O]., where M is titanium or zirconium, Ph is phenyl or substituted phenyl and R is alkyl.

This invention relates to new tetraphosphinates of titanium and zirconium. More particularly, this invention concerns titanium and zirconium tetrakis (diphenylphosphinates) and tetrakis (alkylphenylphosphinates) having the formulae M[OP(Ph) O] and where M is titanium or zirconium, R represents an alkyl group having from one to eight carbon atoms, i.e., methyl, ethyl, isopropyl, butyl, etc., and Ph represents a phenyl radical or monoor multi-substituted phenyl radical wherein the substituents on said phenyl group are independently selected from the group consisting of the halogens and alkyl groups having one to eight carbon atoms. Representative substituted phenyl radicals are, for example, ortho-chlorophenyl, ortho-methylphenyl, pentafluorophenyl, 2,4-dichloropheny1, 2,4-dimethylpheny], ethylphenyl, 2-chloro, 4-methylphenyl and the like.

The tetraphosphinates of this invention are conveniently prepared by reacting the appropriate phosphinic acid, e.g., diphenylphosphinic acid, (C H P(O)OH,-, or an alkylphenylphosphinic acid, i.e., RPhP(O)OH, Ph and R being defined above, with an alkoxide or acetylacetonate of titanium or zirconium, for example, compounds such as M(CH COCHCOCH M(OR) and M(OR) (CH COCHCOCH where M is titanium or zirconium, and R is an alkyl group having from one to four carbon atoms. The foregoing reactions are advantageously carried out in an inert organic diluent for the tetraphosphinate such as benzene, toluene, xylene, chloroform, carbon tetrachloride, tetrachloroethane, and others, at a temperature within the range of about 70 C. to about 145 C. The product is recovered from the reaction mixture by filtration or centrifugation, or by separation from the diluent by distillation of the volatile solvent and by-products, using well known processing techniques.

The titanium and zirconium tetraphosphinates of this invention are useful as additives for hydraulic fluids, oils and the like where, in an amount of about 1 to about 10% of the lubricating fluid, they serve to stabilize its viscosity during temperature fluctuations. The tetraphosphinates also are useful to thicken synthetic lubricant greases derived from diesters of carboxylic acids (such as sebacic, azelaic and adipic acid) and a primary or 0x0 alcohol containing about 8 to 10 carbon atoms. The tetraphosphinate additive is about to about 25% by weight of the diester fluid in the grease compositions.

The following examples illustrate typical preparations of the compounds of this invention.

3,426,050 Patented Feb. 4, 1969 Example 1 2.5 grams of Ti(OC H was added to a suspension of 9.5 grams of diphenylphosphinic acid in 200 ml. of toluene. The reaction mixture was refluxed C.) for about 20 hours. The toluene diluent and by-product ethanol were then removed from the mixture by distillation. The residue was treated with petroleum ether and the ether was evaporated from the extract to yield the pale yellow, solid product Ti[OP(C I-I O] which softened at about C. and became liquid at C.

Analysis.Found: C, 62.52; H, 4.79; P, 13.02; Ti, 5.3. Calculated for C H O P Ti: C, 62.89; H, 4.40; P, 13.52; Ti, 5.2.

This titanium tetraphosphinate is insoluble in water, slightly soluble in hexane, and soluble in ethanol, diethyl ether, acetone and benzene.

Example 2 To 3.12 grams of Zr(CH COCHCOCH in 50 ml. of benzene diluent was added 5.89 grams of Example 3 To a solution of 2.32 grams of Ti(OC H in 200 ml. of benzene was added 637 grams of methylphenylphosphinic acid (CH )(C H )P(O)OH. The reaction mixture was stirred at reflux for 20 hours. The solvent was stripped and the residue was washed with petroleum ether. The solid product, identified as Ti[OP(CH )(C H )O] softened at about 106 C. and became liquid at about 130 C.

Example 4 To a solution of zirconium isopropoxide,

in benzene was added di(ortho-methylphenyl)phosphinic acid, (oCH C H P(O)OH. The vigorously stirred mixture was refluxed for several hours and then the solvent was removed by distillation. The remaining colorless solid was identified as Zr[OP(o-CH C H O] Example 5 A solution of Ti(OC I-I (CH COCHCOCH in toluene was treated with (C F P(O)OH. The vigorously stirred reaction mixture was refluxed for several hours and the solvent removed. The remaining, nearly colorless solid was identified as Ti[OP(C F O] Example 6 To a solution of Ti[OCH(CH in toluene was added di(ortho-propylphenyl)phosphinic acid,

(0-C3Hqc H )2P(O)OH The reaction mixture was stirred and. refluxed. Upon removal of solvent a nearly colorless solid was recovered which was identified as Ti[OP(o-C H C ,-H O],.

3 It is understood that the foregoing examples are illustrative and not limitative of the scope of this invention as defined by the following claims.

I claim: 1. A tetraphosphinate having the formula selected from the class consisting of where M is titanium or zirconium, R represents an alkyl group having from one to eight carbon atoms, and Ph represents a phenyl radical or substituted phenyl radical wherein the substituents on said phenyl group are independently selected from the group consisting of the halogens and alkyl groups having one to eight carbon atoms.

2. A tetraphosphinate of Formula I of claim 1 Wherein M is titanium and Ph represents C H 3. A tetraphosphinate of Formula I of claim 1 Wherein M is Zirconium and Ph represents C H 4 4. A tetraphosphinate of Formula II of claim 1 wherein R is methyl and Ph represents C H 5. A tetraphosphinate of Formula I of claim 1 wherein Ph represents methylphenyl.

5 References Cited UNITED STATES PATENTS 2,228,659 1/1941 Farrington et a1. 260429.5 2,311,306 2/1943 Ritchey 260429.5 0 2,346,155 4/1944 Denison et al. 260429.3

OTHER REFERENCES Izvestia Akak. Nauk SSSR, p. 651 (April 1964), (copy in Group 112 260/4295). 15

HELEN M. MCCARTHEY, Primal Examiner.

H. M, S. SNEED, Assistant Examiner.

20 US. Cl. X.R. 

